CN110172323B - Solvent-resistant epoxy modified polyurethane sealant and preparation method thereof - Google Patents

Solvent-resistant epoxy modified polyurethane sealant and preparation method thereof Download PDF

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CN110172323B
CN110172323B CN201910379792.0A CN201910379792A CN110172323B CN 110172323 B CN110172323 B CN 110172323B CN 201910379792 A CN201910379792 A CN 201910379792A CN 110172323 B CN110172323 B CN 110172323B
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epoxy modified
sealant
modified polyurethane
polyurethane prepolymer
diisocyanate
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CN110172323A (en
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郭盟
李桂妃
张志文
边峰
招兆林
任如飞
谢志明
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Guangdong Shengye Chemical Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

The invention relates to the technical field of sealants, in particular to a solvent-resistant epoxy modified polyurethane sealant and a preparation method thereof, wherein the sealant comprises the following raw materials in percentage by weight: the epoxy modified polyurethane prepolymer A20-40%, the low viscosity polyurethane prepolymer B10-30%, the inorganic filler 29.4-59.4%, the thixotropic agent 0.01-30%, the curing accelerator 0.01-2%, the water removal stabilizer 0.01-2% and the adhesion promoter 0.01-2%. The epoxy modified polyurethane sealant has better chemical corrosion resistance and mechanical property, and through the chemical corrosion resistance test in the industrial standard of the diaphragm gas meter, after being soaked in liquid, the mechanical property, the mass change rate and the volume change rate of the sealant can keep small change rate, the bonding and sealing effects are good, and the epoxy modified polyurethane sealant can also keep good bonding and sealing effects in the long-term use process when being used for the gas meter.

Description

Solvent-resistant epoxy modified polyurethane sealant and preparation method thereof
Technical Field
The invention relates to the technical field of sealing adhesives, in particular to a solvent-resistant epoxy modified polyurethane sealant and a preparation method thereof.
Background
The diaphragm type gas meter is a meter product used for measuring gas in industrial production and resident life, the demand for gas and gas meter is continuously increased along with the improvement of the living standard of people in recent years, the transportation and use safety of the gas is very important due to the inflammable and explosive properties of the gas, major fire and explosion accidents caused by gas leakage reported by various big news media are frequently seen, people are constantly alerted, and the gas tightness of the gas meter is important.
The existing sealing gum for bonding and sealing the gas meter mainly has two categories, one category is the traditional vulcanized rubber sealing washer, the sealing washer has poor bonding property to the meter base material, and only plays a role in simple sealing; the other type is a single-component moisture curing sealant developed in recent years, which mainly comprises silicone, polyurethane, modified silane and the like, wherein the polyurethane sealant is widely applied to bonding and sealing of gas meters due to excellent mechanical property and bonding property, and has the main characteristics of convenient construction, capability of sizing a groove part with any shape and quick curing.
However, the traditional polyurethane sealant has the problems of aging of the sealant and failure of bonding and sealing in the long-term use process, which leads to air leakage of a gas meter and has great potential safety hazard. The reason for this problem is, on the one hand, the normal ageing of the natural environment and, on the other hand, the very important reason for the poor solvent resistance of the sealants. As is well known, the main components of gases such as natural gas, coal gas, liquefied petroleum gas and the like are hydrocarbon substances, and the liquefied gas can corrode a gas meter to a certain extent and corrode a sealant after long-term contact, so that gas leakage of the gas meter is caused. Therefore, in order to solve the problem of air leakage of the gas meter in the long-term use process, a polyurethane adhesive sealant with excellent solvent resistance and good adhesive sealing property is urgently needed to be found.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide the solvent-resistant epoxy modified polyurethane sealant which is resistant to chemical corrosion, and has the advantages that the mechanical property, the mass change rate and the volume change rate of the sealant can be kept at small change rates after being soaked in liquid, and the bonding and sealing effects are good.
The invention also aims to provide a preparation method of the solvent-resistant epoxy modified polyurethane sealant, which has the advantages of simple operation, convenient control, production cost reduction, high product quality, chemical corrosion resistance of the prepared polyurethane sealant, good mechanical property and good bonding and sealing effects, and can be used for large-scale production.
The purpose of the invention is realized by the following technical scheme: a solvent-resistant epoxy modified polyurethane sealant comprises the following raw materials in percentage by weight:
Figure BDA0002052982270000021
the polyurethane sealant prepared by the raw materials has better chemical corrosion resistance and mechanical property, and through a chemical corrosion resistance test in the industrial standard (GB/T6968-.
In addition, the polyurethane sealant sold in the market at present generally uses conventional plasticizers such as DOP, DBP and macromolecular plasticizers to plasticize products, so that the viscosity, hardness and mechanical properties of the products can be improved, but most of the polyurethane sealant is micromolecular compounds or linear macromolecules, the polyurethane sealant does not participate in chemical reaction in a sealant system, a firm mesh structure is formed, and the polyurethane sealant slowly precipitates along with the soaking of a solvent after a long time due to the common physical mixing, so that the bonding capability and the sealing property of the sealant are reduced. The invention adopts the polyurethane prepolymer B with low viscosity and NCO end to adjust the viscosity of the sealant and improve the hardness of the sealant, and forms a permanent cured product structure together with the epoxy modified polyurethane prepolymer A through moisture curing reaction, thereby solving the problems that the viscosity, the mechanical property and the hardness of the sealant are adjusted by adding a plasticizer, solving the problem that the plasticizer is easy to separate out, and further improving the solvent resistance of the whole sealant.
The adopted inorganic filler can improve the strength of the sealant, promote the dispersion of materials, ensure that the mechanical property, the mass change rate and the volume change rate of the sealant can be kept at a small change rate after the sealant is soaked in liquid, and reduce the production cost; the adopted thixotropic agent can improve the good fluidity and uniformity of the sealant under external forces such as stirring or shearing, so that the sealant is easy to glue, and after the external force is removed, the sealant can recover a state which is difficult to flow, the viscosity is high, the sealant is prevented from flowing on an inclined plane or a vertical plane, and the stability of the sealant is improved; the adopted curing accelerator can promote the curing reaction of the sealant material and improve the curing efficiency; the adopted dehydration stabilizer can remove residual moisture in a polyurethane sealant two-component moisture curing system, eliminate the foaming and pinhole phenomena of the sealant, improve the wear resistance and the adhesiveness of the sealant and improve the chemical corrosion resistance of the sealant; the adopted adhesion promoter has better compatibility with the epoxy modified polyurethane prepolymer A and the low-viscosity polyurethane prepolymer B, promotes the cross-linking coupling reaction between the materials, and improves the adhesive force and the adhesive strength between the sealant and the surface of the base material.
Preferably, the epoxy modified polyurethane prepolymer A is an NCO-terminated polymer prepared by reacting the following raw materials in percentage by weight: 15-40% of polyether triol, 20-45% of epoxy modified polyether triol and 20-40% of diisocyanate; wherein the molar ratio of isocyanate group to hydroxyl group of the epoxy modified polyurethane prepolymer A is 2.0-3.0: 1.
according to the invention, the epoxy modified polyurethane prepolymer A is prepared by adopting the raw materials, and the dosage of each material and the molar ratio of the groups are strictly controlled, so that the prepared epoxy modified polyurethane prepolymer A has excellent cohesive energy strength, mechanical property and solvent soaking resistance.
Preferably, the polyether triol is a polyoxypropylene triol with an average molecular weight of 2000-6000; the diisocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate and p-phenylene diisocyanate.
The main chain of the polyoxypropylene triol adopted by the invention contains ether bond (-R-O-R-), and the end group or the side group contains three hydroxyl (-OH), so that diisocyanate can be catalyzed, the crosslinking reaction of the polyurethane prepolymer is promoted, and the prepared sealant has excellent water resistance, impact resistance and low temperature property; the diisocyanate is high in activity and can be efficiently crosslinked with polyether triol and epoxy modified polyether triol to form the epoxy modified polyurethane prepolymer A with a stable network structure.
Preferably, the epoxy modified polyether triol is an OH-terminated compound prepared by reacting trifunctional glycidyl epoxy resin with polyethylene glycol, wherein the molar ratio of epoxy groups to hydroxyl groups is 1: 1.5-2.5; the trifunctional glycidyl epoxy resin is glycidyl ether epoxy resin or glycidyl amine epoxy resin; the molecular weight of the polyethylene glycol is 500-3000.
According to the invention, trifunctional glycidyl epoxy resin is adopted to react with polyethylene glycol to prepare epoxy modified polyether triol, and the molar ratio of epoxy group to hydroxyl is strictly controlled, so that the prepared epoxy modified polyether triol has more rigid structures and reaction crosslinking points compared with the currently marketed bisphenol A modified polyether diol, and is subjected to crosslinking reaction with polyether triol and diisocyanate to form epoxy modified polyurethane prepolymer A with stable network structure, the cohesive energy strength of the epoxy modified polyurethane prepolymer A can be obviously improved, and the strength and solvent resistance of the prepared sealant are further improved.
The glycidyl ether epoxy resin or glycidyl amine epoxy resin has multiple functions, high activity, high crosslinking density, high heat resistance, strong binding power, corrosion resistance and excellent mechanical strength, and the reaction with polyethylene glycol can ensure that the epoxy modified polyether triol has better rigidity characteristic and excellent corrosion resistance. More preferably, the glycidyl ether epoxy resin is triglycidyl isocyanurate.
Preferably, the low-viscosity polyurethane prepolymer B is an NCO-terminated polymer prepared by reacting the following raw materials in percentage by weight: 40-80% of polyether glycol and 20-60% of diisocyanate; wherein the molar ratio of isocyanate group to hydroxyl group of the low-viscosity polyurethane prepolymer B is 2.5-3.0: 1; the viscosity of the low-viscosity polyurethane prepolymer B is 1000-3000mPa & s.
According to the invention, polyether diol and diisocyanate are adopted for cross-linking polymerization, and the use amount of each material and the molar ratio of the groups are strictly controlled, so that the prepared low-viscosity polyurethane prepolymer B has narrower relative molecular weight distribution and lower viscosity (1000-3000 mPa & s), and can be used as an internal plasticizer in the sealant for adjusting the viscosity and the hardness of the sealant.
Preferably, the polyether diol is polyoxypropylene diol having an average molecular weight of 500-2000; the diisocyanate is at least one of toluene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.
The main chain of the polyoxypropylene glycol adopted by the invention contains ether bond (-R-O-R-), and the end group or the side group contains two hydroxyl groups (-OH), so that the polymerization reaction of diisocyanate can be catalyzed, the crosslinking effect of a polyurethane prepolymer is promoted, and the prepared sealant has excellent water resistance, impact resistance and low temperature property; the diisocyanate is high in activity and can be efficiently crosslinked with polyether diol to form a low-viscosity polyurethane prepolymer B with a stable network structure.
Preferably, the inorganic filler is at least one of nano calcium carbonate, kaolin, silicon micropowder and carbon black with the moisture content of less than 500ppm after drying; the thixotropic agent is at least one of fumed silica, polyurea, bentonite and PVC powder with the moisture content of less than 500ppm after drying; the water removal stabilizer is at least one of oxazolidine water removal agent, p-methyl benzenesulfonyl isocyanate and triethyl orthoformate.
The inorganic filler can be uniformly dispersed in a sealant system, the powder structure of the inorganic filler can effectively promote the dispersion uniformity of other materials, the mechanical property, the mass change rate and the volume change rate of the prepared sealant can be kept to be very small after the sealant is soaked in liquid, and the production cost of the sealant is reduced.
The thixotropic agent can be uniformly dispersed in a sealant system by adopting the thixotropic agent, the powder structure of the thixotropic agent can effectively promote the dispersion uniformity of other materials, and the prepared sealant has better fluidity and uniformity under external forces such as stirring or shearing, so that the sealant is easy to glue, and after the external force is removed, the sealant recovers a state which is difficult to flow, has higher viscosity, prevents the sealant from flowing on an inclined plane or a vertical plane, and improves the stability of the sealant; the adopted gas-phase silicon dioxide is not subjected to surface treatment, contains a plurality of undisturbed free hydrogen bonds and a plurality of continuous bonding hydrogen bonds which form hydrogen bonds with each other, and is mixed and reacted with the epoxy modified polyurethane prepolymer A, the low-viscosity polyurethane prepolymer B, the inorganic filler and other materials to form the mutually cross-linked hydrogen bonds, so that a three-dimensional reticular structure is formed, the three-dimensional reticular structure is damaged under the influence of external mechanical force, the viscosity is reduced, the sealant recovers good fluidity, the three-dimensional reticular structure can recover in a shape after the external mechanical force is eliminated, the viscosity of the sealant is increased, the sealant is not easy to flow, and the sagging phenomenon in a cured sealant layer can be prevented, so that the sizing is uniform; the adopted polyurea and epoxy modified polyurethane sealant system is selectively incompatible, fine and needle-shaped crystals are generated, a three-dimensional network structure is formed through bonding force among the crystals, the network structure is damaged under external force, the viscosity of the sealant is rapidly reduced, the network structure can be restored under the external force, the viscosity is increased, and the polyurea can play a role in rheological control after a small amount of polyurea is added, so that the cost of materials is reduced; the adopted bentonite can enable the sealant to have pseudoplastic flow, the anti-sagging property is good, the recovery speed of the rheological property of the sealant after external force is removed is high, the recovery time is short, and the stable state can be quickly recovered.
The moisture content of the dried inorganic filler and the dried thixotropic agent is strictly controlled, so that the phenomena of agglomeration and uneven dispersion of raw materials caused by excessive moisture can be avoided, the moisture in the production process of the sealant is reduced, on one hand, the addition of a subsequent dewatering stabilizer is reduced, the quality influence of the subsequent dewatering stabilizer on the sealant is reduced, the cost of the raw materials is reduced, on the other hand, the prepared sealant has better viscosity and rheological property, the flowability is good under the action of external force, the sizing is easy, the sealant is not easy to flow after the external force is removed, the flow is not easy, and the sealing property and the adhesiveness of the sealant are improved.
By adopting the dewatering stabilizer, residual moisture in a two-component moisture curing system of the polyurethane sealant can be removed, the foaming and pinhole phenomena of the sealant are eliminated, the wear resistance and the adhesion of the sealant are improved, and the chemical corrosion resistance of the sealant is improved; wherein, the adopted oxazolidine water remover indirectly reacts with isocyanate, the functionality is 2, the moisture in the system is removed by decomposing the oxazolidine sensitive to the moisture and consuming the moisture, and the curing of the polyurethane prepolymer A and the polyurethane prepolymer B with low NCO content can be promoted; the adopted p-methyl benzenesulfonyl isocyanate is monofunctional group isocyanate, has higher activity, preferentially reacts with moisture in the toluene diisocyanate, the hexamethylene diisocyanate, the polyether triol, the epoxy modified polyether triol and the polyether diol to generate carbamate, does not increase the viscosity of a system, and further realizes the action of removing the moisture in the system, and carbon dioxide generated in the reaction process of the p-methyl benzenesulfonyl isocyanate and the moisture in the system is removed by subsequent vacuum bubble removal; and the adopted triethyl orthoformate can be slightly soluble in water and decompose the water in the system, so that the consumption and removal of the water in the system are realized.
Preferably, the curing accelerator is at least one of an organotin catalyst, a tertiary amine catalyst, an organozinc catalyst and an organobismuth catalyst; the adhesion promoter is at least one of epoxy silane coupling agent, amino silane coupling agent and mercapto silane coupling agent.
By adopting the curing agent of the type, the curing reaction of the sealant material can be promoted, and the curing efficiency is improved; the adopted organic tin catalyst reduces the influence of temperature on the catalytic activity due to the steric hindrance effect of the organic tin catalyst, and has higher stability, hydrolysis resistance and delayed catalytic activity; the adopted tertiary amine catalyst has main catalytic action on the reactions of-NCO and water, as well as-NCO, hydroxyl-terminated polyester and polyether polyol generated in a polyurethane sealant system, can promote the polymer molecular chain to rapidly grow, rapidly increase the viscosity and rapidly improve the network skeleton strength of the sealant; the adopted organic zinc catalyst can catalyze the reaction of hydroxyl and isocyanate, has obvious activity on the subsequent crosslinking, curing and later strength rise of polyurethane, and can improve the catalytic activity when being used together with the organic bismuth catalyst; the adopted organic bismuth catalystHas excellent stability against hydrolysis, reduces the selectivity of reaction with water, reduces the side reaction of water and-NCO group in the system, promotes the promotion of-NCO/-OH reaction, avoids-NCO side reaction, reduces CO2The subsequent vacuum bubble removal process is reduced, the synergistic effect is achieved by combining the organic bismuth catalyst, the catalytic activity and the process flexibility are improved, and the energy consumption and the production cost are reduced.
By adopting the adhesion promoter, the compatibility with the epoxy modified polyurethane prepolymer A and the low-viscosity polyurethane prepolymer B is better, the cross-linking coupling reaction between the materials is promoted, and the adhesive force and the adhesive strength between the sealant and the surface of the base material are improved; the adopted epoxy silane coupling agent has stable storage and non-yellowing adhesion promotion effect, and can remarkably improve the adhesion, water resistance and solvent resistance of the sealant on a sizing matrix; the adopted aminosilane coupling agent has better compatibility with the epoxy modified polyurethane prepolymer A and the low-viscosity polyurethane prepolymer B, and can improve long-time excellent adhesiveness, water resistance, solvent corrosion resistance and salt fog resistance; the adopted mercapto silane coupling agent can enable the sealant to have photopolymerization reaction of carbon-carbon double bonds, generate double crosslinking curing with a sealant system, and can generate nucleophilic addition reaction with polyurethane, so that the corrosion resistance and the adhesion of the sealant are improved under the actions of photocuring and double-component crosslinking curing.
Preferably, the organic tin catalyst is at least one of dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, alkyl tin mercaptide, dioctyltin mercaptide and dialkyl tin dimaleate; the tertiary amine catalyst is at least one of N, N-dimethylcyclohexylamine, triethanolamine, dimethylethanolamine, triethylamine and triethylenediamine; the organic zinc catalyst is at least one of zinc isooctanoate, zinc neodecanoate and zinc naphthenate; the organic bismuth catalyst is at least one of bismuth isooctanoate, bismuth laurate, bismuth neodecanoate and bismuth naphthenate; the epoxy silane coupling agent is at least one of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, 3- (2, 3-epoxypropoxy) propyl methyl diethoxy silane, 2- (3, 4-epoxycyclohexyl) ethyl triethoxy silane and 2- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane; the amino silane coupling agent is at least one of gamma-aminopropyl triethoxysilane, N-beta (aminoethyl) -gamma-aminopropyl trimethoxysilane, phenylaminomethyl triethoxysilane and N-beta (aminoethyl) -gamma-aminopropyl methyl diethoxy silane; the mercaptosilane coupling agent is gamma-mercaptopropyltrimethoxysilane.
By adopting the organic tin catalyst, the influence of temperature on the catalytic activity of the organic tin catalyst is reduced due to the steric hindrance effect of the organic tin catalyst, and the organic tin catalyst has higher stability, hydrolysis resistance and delayed catalytic activity; the adopted dialkyl tin dimaleate and dithiol alkyl tin can improve the hydrolytic stability of the sealant; the adopted dioctyl tin mercaptide contains large alkyl groups, can improve the stability of the sealant, and has the performance of delaying catalysis.
By adopting the tertiary amine catalyst, the main catalytic action is played on the reactions of-NCO and water, as well as-NCO, hydroxyl-terminated polyester and polyether polyol which are generated in a polyurethane sealant system, so that the polymer molecular chain can be promoted to grow rapidly, the viscosity can be increased rapidly, and the network framework strength of the sealant can be improved rapidly; the dimethyl ethanolamine has a tertiary amine group and a hydroxyl group, has a very strong catalytic effect on polyurethane prepolymer generated by isocyanate polymerization, and the hydroxyl group in the dimethyl ethanolamine can react with isocyanate, so that the dimethyl ethanolamine can be chemically adhered to the polyurethane polymer, and the pungent smell of the sealant is reduced; the adopted triethylamine has strong alkalinity, small steric effect and excellent catalytic activity; two nitrogen atoms of the adopted triethylene diamine are connected to three ethylene groups to form a cage structure of a double-ring molecule with a compact and symmetrical structure, and meanwhile, no substituent group is connected to the nitrogen atoms, so that a pair of empty electrons on the completely exposed nitrogen atoms can be more easily close to-NCO groups, an extremely unstable complex is generated, and the catalyst plays an excellent catalytic role in the reaction of isocyanate.
By adopting the organic zinc catalyst, the reaction of hydroxyl and isocyanate can be catalyzed, and the subsequent polyurethane can be treatedThe crosslinking, curing and later strength increase of the ester have remarkable activity. By adopting the organic bismuth catalyst, the hydrolysis resistance stability is excellent, the selectivity of the reaction with water is reduced, the side reaction of water and-NCO in the system is reduced, the promotion of the reaction of-NCO/-OH is promoted, the side reaction of-NCO is avoided, and CO is reduced2The subsequent vacuum bubble removal process is reduced.
The other purpose of the invention is realized by the following technical scheme: the preparation method of the solvent-resistant epoxy modified polyurethane sealant comprises the following steps:
step (1), preparing an epoxy modified polyurethane prepolymer A: according to the weight percentage, mixing polyether triol and epoxy modified polyether triol, heating to 110 ℃ with temperature, vacuumizing to remove water, cooling to 80-90 ℃, adding diisocyanate, reacting under the protection of nitrogen, and cooling to room temperature until the NCO value is unchanged to obtain epoxy modified polyurethane prepolymer A;
step (2), preparing a low-viscosity polyurethane prepolymer B: heating polyether glycol to 110 ℃ according to the weight percentage, vacuumizing to remove water, cooling to room temperature, slowly and uniformly dripping the polyether glycol into diisocyanate, controlling the dripping time to be 0.8-1.2h, reacting for 4-6h under the protection of nitrogen at the temperature of 80-90 ℃, and cooling to room temperature when the NCO value is unchanged to prepare a low-viscosity polyurethane prepolymer B;
step (3), preparing the epoxy modified polyurethane sealant: according to the weight percentage, uniformly stirring the epoxy modified polyurethane prepolymer A prepared in the step (1), the low-viscosity polyurethane prepolymer B prepared in the step (2), the inorganic filler and the thixotropic agent under the vacuum state of-0.098 to-0.1 Mpa, keeping the mixing temperature at 10-50 ℃, then sequentially adding the curing accelerator, the adhesion accelerator and the dewatering stabilizer, uniformly stirring, removing bubbles under the vacuum state of-0.098 to-0.1 Mpa, and removing the vacuum by using dry nitrogen gas to obtain the solvent-resistant epoxy modified polyurethane adhesive sealant.
The solvent-resistant epoxy modified polyurethane adhesive sealant prepared by the steps is simple to operate, convenient to control, low in production cost, high in product quality, resistant to chemical corrosion, solvent-resistant, good in mechanical property and good in adhesive sealing effect, and can be used for large-scale production; in the process for preparing the epoxy modified polyurethane prepolymer A, epoxy modified polyether triol synthesized by trifunctional glycidyl epoxy resin and polyethylene glycol is adopted, compared with bisphenol A modified polyether diol sold in the market at present, the epoxy modified polyurethane prepolymer A has more rigid structures and reaction crosslinking points, so that the prepared epoxy modified polyurethane prepolymer A has excellent cohesive energy strength, mechanical property and solvent soaking resistance.
In the process for preparing the low-viscosity polyurethane prepolymer B, the polyether diol is slowly dripped into the diisocyanate solution, the dripping time (dripping speed) is controlled, compared with the conventional one-pot method, the prepared prepolymer B has narrower relative molecular mass distribution and lower viscosity, and the prepolymer B is used as an internal plasticizer of the sealant to adjust the viscosity and hardness of the sealant; and the polyether diol is heated and vacuum dewatered to react the subsequently added diisocyanate-NCO group with-OH in the system without side reaction with water in the system, so that the polyurethane prepolymer B with high purity and stable quality is prepared.
In the process for preparing the sealant, the epoxy modified polyurethane prepolymer A, the low-viscosity polyurethane prepolymer B, the inorganic filler and the thixotropic agent are stirred under vacuum to uniformly disperse the inorganic filler and the thixotropic agent in a polyurethane system, the rheological property of the epoxy modified polyurethane prepolymer A and the low-viscosity polyurethane prepolymer B is changed by external stirring under the action of the thixotropic agent to promote the dispersion of materials, and then the curing accelerator, the adhesion accelerator and the dewatering stabilizer are sequentially added to promote the cross-linking polymerization reaction between the epoxy modified polyurethane prepolymer A and the low-viscosity polyurethane prepolymer B and promote the bonding strength of the system, so that the prepared sealant has better adhesive force and adhesive force to a gluing matrix, and simultaneously dewaters to avoid byproducts generated by water and isocyanate in the system to influence the quality of the sealant, eliminate the foaming and pinhole phenomena of the sealant and improve the wear resistance and the adhesiveness of the sealant, the chemical corrosion resistance of the sealant is improved.
The invention has the beneficial effects that: the epoxy modified polyurethane adhesive sealant has better chemical corrosion resistance and mechanical property, and through a chemical corrosion resistance test in the industrial standard (GB/T6968-.
The preparation method of the epoxy modified polyurethane bonding sealant has the advantages of simple operation, convenient control, reduced production cost, high product quality, chemical corrosion resistance, solvent resistance, good mechanical property and good bonding and sealing effects of the prepared polyurethane sealant, and can be used for large-scale production.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
A preparation method of solvent-resistant epoxy modified polyurethane sealant comprises the following steps:
step (1), preparing an epoxy modified polyurethane prepolymer A: adding 360g of epoxy modified polyether triol and 480g of polyether triol (relative molecular weight is 5000) into a dry 2L four-mouth bottle in sequence, heating to 100 ℃, carrying out vacuum dehydration for 2h, cooling to 80 ℃ after detecting that the moisture content of the liquid material is less than or equal to 100ppm, adding 280g of benzhydryl diisocyanate, carrying out heat preservation reaction for 5h under the protection of nitrogen, cooling to room temperature when the NCO value is unchanged, discharging to obtain an epoxy modified polyurethane prepolymer A, and placing the epoxy modified polyurethane prepolymer A in a dry nitrogen sealed container for later use.
Step (2), preparing a low-viscosity polyurethane prepolymer B: placing 800g of polyether glycol in a single-neck bottle, heating to 100 ℃, vacuumizing for dehydration, cooling to room temperature after the moisture content is less than 100ppm, transferring to a separating funnel, dropwise adding into a four-neck flask containing a mixture of 240g of isophorone diisocyanate and 2g of catalyst stannous octoate at a constant speed, controlling the dropwise adding speed at 1h, reacting at a constant temperature of 80 ℃ for 6h under the protection of nitrogen, cooling to room temperature when the NCO value is unchanged, discharging to obtain a low-viscosity polyurethane prepolymer B, and placing in a dry nitrogen sealed container for later use.
Step (3), preparing the epoxy modified polyurethane sealant: adding 280g of the epoxy modified polyurethane prepolymer A prepared in the step (1), 220g of the low-viscosity polyurethane prepolymer B prepared in the step (2), 300g of nano calcium carbonate, 150g of PVC powder, 20g of fumed silica and 20g of carbon black into a planetary stirring kettle, uniformly stirring under the vacuum state of-0.098 Mpa, keeping the stirring and mixing temperature at less than 50 ℃, then removing the vacuum by using dry nitrogen, sequentially adding 1g of curing accelerator, 4g of bonding accelerator and 5g of dewatering stabilizer, vacuumizing under reduced pressure, removing bubbles under the vacuum state of-0.098 Mpa, then removing the vacuum by using dry nitrogen, pouring, preparing solvent-resistant epoxy modified polyurethane bonding sealant, and loading into a closed container.
In the step (1), the preparation method of the epoxy modified polyether triol comprises the following steps: 150g of polyethylene glycol (with a relative molecular weight of 500) and 29.7g of glycidyl ether epoxy resin are added into a dry 1L four-mouth bottle, the temperature is raised to 80 ℃, 0.9g of catalyst boron trifluoride is added, the reaction is carried out for 4 hours at a constant temperature, after infrared detection, the reaction is terminated after the epoxy group peak completely disappears, the temperature is reduced, and the epoxy modified polyether triol is prepared.
Wherein the glycidyl ether epoxy resin is triglycidyl isocyanurate.
In the step (1), the polyether triol is a polyoxypropylene triol.
In the step (2), the polyether glycol is polyoxypropylene glycol having an average molecular weight of 500.
In the step (3), the nano calcium carbonate, the PVC powder, the fumed silica and the carbon black are all dried in advance until the moisture content is less than 500 ppm.
In the step (3), the curing accelerator is dibutyltin dilaurate; the adhesion promoter is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane; the water removal stabilizer is p-toluenesulfonyl isocyanate.
Example 2
A preparation method of solvent-resistant epoxy modified polyurethane sealant comprises the following steps:
step (1), preparing an epoxy modified polyurethane prepolymer A: adding 522g of epoxy modified polyether triol and 174g of polyether triol (relative molecular weight of 5000) into a dry 2L four-mouth bottle in sequence, heating to 100 ℃, carrying out vacuum dehydration for 2 hours, cooling to 85 ℃ after detecting that the moisture content of the liquid material is less than or equal to 100ppm, adding 464g of toluene diisocyanate, carrying out heat preservation reaction for 5 hours under the protection of nitrogen, cooling to room temperature when the NCO value is unchanged, discharging to obtain an epoxy modified polyurethane prepolymer A, and placing the epoxy modified polyurethane prepolymer A in a dry nitrogen sealed container for later use.
Step (2), preparing a low-viscosity polyurethane prepolymer B: placing 800g of polyether glycol in a single-neck bottle, heating to 105 ℃, vacuumizing for dehydration, cooling to room temperature after the moisture content is less than 100ppm, transferring to a separating funnel, dropwise adding into a four-neck flask containing 200g of toluene diisocyanate and 2g of catalyst stannous octoate mixture at constant speed, controlling the dropwise adding speed at 0.8h, reacting at constant temperature for 5h under the protection of nitrogen at 80 ℃, cooling to room temperature when the NCO value is unchanged, discharging to obtain a low-viscosity polyurethane prepolymer B, and placing in a dry nitrogen sealed container for later use.
Step (3), preparing the epoxy modified polyurethane sealant: adding 400g of the epoxy modified polyurethane prepolymer A prepared in the step (1), 100g of the low-viscosity polyurethane prepolymer B prepared in the step (2), 300g of nano calcium carbonate, 150g of polyurea, 20g of fumed silica and 20g of kaolin into a planetary stirring kettle, uniformly stirring under the vacuum state of-0.099 Mpa, keeping the stirring and mixing temperature at less than 30 ℃, then removing the vacuum by using dry nitrogen, sequentially adding 1g of curing accelerator, 4g of bonding accelerator and 5g of dewatering stabilizer, vacuumizing under reduced pressure, removing bubbles under the vacuum state of-0.099 Mpa, then removing the vacuum by using dry nitrogen, pouring, preparing the solvent-resistant epoxy modified polyurethane bonding sealant, and loading the solvent-resistant epoxy modified polyurethane bonding sealant into a closed container.
In the step (1), the preparation method of the epoxy modified polyether triol comprises the following steps: adding 800g of polyethylene glycol (with a relative molecular weight of 500) and 29.7g of glycidyl ether epoxy resin into a dry 1L four-mouth bottle, heating to 80 ℃, adding 0.9g of catalyst boron trifluoride, reacting for 4 hours at a constant temperature, stopping the reaction after an epoxy group peak completely disappears through infrared detection, cooling and discharging to obtain the epoxy modified polyether triol.
Wherein the glycidyl ether epoxy resin is triglycidyl isocyanurate.
In the step (1), the polyether triol is a polyoxypropylene triol.
In the step (2), the polyether glycol is polyoxypropylene glycol having an average molecular weight of 1000.
In the step (3), the nano calcium carbonate, the polyurea, the fumed silica and the kaolin are all dried in advance until the moisture content is less than 500 ppm.
In the step (3), the curing accelerator is N, N-dimethylcyclohexylamine; the adhesion promoter is gamma-mercaptopropyl-trimethoxysilane; the water removal stabilizer is an oxazolidine water removal agent.
Example 3
A preparation method of solvent-resistant epoxy modified polyurethane sealant comprises the following steps:
step (1), preparing an epoxy modified polyurethane prepolymer A: sequentially adding 232g of epoxy modified polyether triol and 464g of polyether triol (relative molecular weight of 5000) into a dry 2L four-mouth bottle, heating to 110 ℃, carrying out vacuum dehydration for 2h, cooling to 90 ℃ after detecting that the moisture content of the liquid material is less than or equal to 100ppm, adding 464g of p-phenylene diisocyanate, carrying out heat preservation reaction for 5h under the protection of nitrogen, cooling to room temperature when the NCO value is unchanged, discharging to obtain an epoxy modified polyurethane prepolymer A, and placing the epoxy modified polyurethane prepolymer A in a dry nitrogen sealed container for later use.
Step (2), preparing a low-viscosity polyurethane prepolymer B: 400g of polyether glycol is placed in a single-neck bottle, the temperature is raised to 110 ℃, the vacuum pumping dehydration is carried out, the temperature is reduced to room temperature after the moisture content is less than 100ppm, the polyether glycol is moved to a separating funnel, the polyether glycol is dripped into a four-neck flask containing 600g of hexamethylene diisocyanate and 2g of catalyst stannous octoate mixture at a constant speed, the dripping speed is controlled to be 1.2h, the constant temperature reaction is carried out for 4h under the protection of nitrogen at the temperature of 90 ℃, the temperature is reduced to room temperature when the NCO value is unchanged, the polyurethane prepolymer B with low viscosity is prepared by discharging, and the polyurethane prepolymer B is placed in a dry nitrogen closed container for standby.
Step (3), preparing the epoxy modified polyurethane sealant: adding 200g of the epoxy modified polyurethane prepolymer A prepared in the step (1), 300g of the low-viscosity polyurethane prepolymer B prepared in the step (2), 200g of silicon powder, 20g of polyurea, 20g of bentonite and 200g of kaolin into a planetary stirring kettle, uniformly stirring under the vacuum state of-0.1 Mpa, keeping the stirring and mixing temperature at less than 10 ℃, then removing vacuum by using dry nitrogen, sequentially adding 20g of curing accelerator, 20g of bonding accelerator and 20g of dewatering stabilizer, vacuumizing under reduced pressure, removing bubbles under the vacuum state of-0.1 Mpa, removing vacuum by using dry nitrogen, discharging, obtaining the solvent-resistant epoxy modified polyurethane bonding sealant, and loading into a closed container.
In the step (1), the preparation method of the epoxy modified polyether triol comprises the following steps: 300g of polyethylene glycol (with a relative molecular weight of 1000) and 29.7g of glycidylamine epoxy resin are added into a dry 1L four-mouth bottle, the temperature is raised to 80 ℃, 0.9g of catalyst boron trifluoride is added, the reaction is carried out for 4 hours at constant temperature, after infrared detection, the reaction is terminated after the epoxy group peak completely disappears, the temperature is reduced, and the epoxy modified polyether triol is prepared.
In the step (1), the polyether triol is a polyoxypropylene triol.
In the step (2), the polyether glycol is polyoxypropylene glycol having an average molecular weight of 1500.
In the step (3), the silica micropowder, the polyurea, the bentonite and the kaolin are all dried in advance until the moisture content is less than 500 ppm.
In the step (3), the curing accelerator is zinc isooctanoate; the adhesion promoter is N-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane, and the water removal stabilizer is triethyl orthoformate.
Example 4
A preparation method of solvent-resistant epoxy modified polyurethane sealant comprises the following steps:
step (1), preparing an epoxy modified polyurethane prepolymer A: sequentially adding 480g of epoxy modified polyether triol and 360g of polyether triol (relative molecular weight is 5000) into a dry 2L four-mouth bottle, heating to 100 ℃, carrying out vacuum dehydration for 2h, cooling to 80 ℃ after detecting that the moisture content of the liquid material is less than or equal to 100ppm, adding 300g of benzhydryl diisocyanate, carrying out heat preservation reaction for 4h under the protection of nitrogen, cooling to room temperature when the NCO value is unchanged, discharging to obtain an epoxy modified polyurethane prepolymer A, and placing the epoxy modified polyurethane prepolymer A in a dry nitrogen sealed container for later use.
Step (2), preparing a low-viscosity polyurethane prepolymer B: placing 800g of polyether glycol in a single-neck bottle, heating to 102 ℃, vacuumizing for dehydration, cooling to room temperature after the moisture content is less than 100ppm, transferring to a separating funnel, dropwise adding into a four-neck flask containing a mixture of 240g of isophorone diisocyanate and 2g of catalyst stannous octoate at a constant speed, controlling the dropwise adding speed at 1h, reacting at a constant temperature of 80 ℃ for 6h under the protection of nitrogen, cooling to room temperature when the NCO value is unchanged, discharging to obtain a low-viscosity polyurethane prepolymer B, and placing the low-viscosity polyurethane prepolymer B in a dry nitrogen sealed container for later use.
Step (3), preparing the epoxy modified polyurethane sealant: adding 280g of the epoxy modified polyurethane prepolymer A prepared in the step (1), 220g of the low-viscosity polyurethane prepolymer B prepared in the step (2), 300g of nano calcium carbonate, 150g of PVC powder, 20g of fumed silica and 20g of carbon black into a planetary stirring kettle, uniformly stirring under the vacuum state of-0.098 Mpa, keeping the stirring and mixing temperature at less than 50 ℃, then removing the vacuum by using dry nitrogen, sequentially adding 1g of curing accelerator, 4g of bonding accelerator and 5g of dewatering stabilizer, vacuumizing under reduced pressure, removing bubbles under the vacuum state of-0.098 Mpa, then removing the vacuum by using dry nitrogen, pouring, obtaining solvent-resistant epoxy modified polyurethane bonding sealant, and loading the solvent-resistant epoxy modified polyurethane bonding sealant into a closed container.
In the step (1), the preparation method of the epoxy modified polyether triol comprises the following steps: 150g of polyethylene glycol (with a relative molecular weight of 500) and 29.7g of glycidyl ether epoxy resin are added into a dry 1L four-mouth bottle, the temperature is raised to 80 ℃, 0.9g of catalyst boron trifluoride is added, the reaction is carried out for 4 hours at a constant temperature, after infrared detection, the reaction is terminated after the epoxy group peak completely disappears, the temperature is reduced, and the epoxy modified polyether triol is prepared.
Wherein the glycidyl ether epoxy resin is triglycidyl isocyanurate.
In the step (1), the polyether triol is a polyoxypropylene triol.
In the step (2), the polyether glycol is a polyoxypropylene glycol having an average molecular weight of 2000.
In the step (3), the nano calcium carbonate, the PVC powder, the fumed silica and the carbon black are all dried in advance until the moisture content is less than 500 ppm.
In the step (3), the curing accelerator is dibutyltin dilaurate, the adhesion promoter is gamma- (2, 3-glycidoxy) propyl trimethoxy silane, and the water removal stabilizer is toluene sulfonyl isocyanate.
Example 5
A preparation method of solvent-resistant epoxy modified polyurethane sealant comprises the following steps:
step (1), preparing an epoxy modified polyurethane prepolymer A: adding 360g of epoxy modified polyether triol and 480g of polyether triol (relative molecular weight is 5000) into a dry 2L four-mouth bottle in sequence, heating to 100 ℃, carrying out vacuum dehydration for 2h, cooling to 80 ℃ after detecting that the moisture content of the liquid material is less than or equal to 100ppm, adding 280g of benzhydryl diisocyanate, carrying out heat preservation reaction for 5h under the protection of nitrogen, cooling to room temperature when the NCO value is unchanged, discharging to obtain an epoxy modified polyurethane prepolymer A, and placing the epoxy modified polyurethane prepolymer A in a dry nitrogen sealed container for later use.
Step (2), preparing a low-viscosity polyurethane prepolymer B: placing 800g of polyether glycol in a single-neck bottle, heating to 100 ℃, vacuumizing for dehydration, cooling to room temperature after the moisture content is less than 100ppm, transferring to a separating funnel, dropwise adding into a four-neck flask containing a mixture of 240g of isophorone diisocyanate and 2g of catalyst stannous octoate at a constant speed, controlling the dropwise adding speed at 1h, reacting at a constant temperature of 80 ℃ for 6h under the protection of nitrogen, cooling to room temperature when the NCO value is unchanged, discharging to obtain a low-viscosity polyurethane prepolymer B, and placing in a dry nitrogen sealed container for later use.
Step (3), preparing the epoxy modified polyurethane sealant: adding 220g of the epoxy modified polyurethane prepolymer A prepared in the step (1), 280g of the low-viscosity polyurethane prepolymer B prepared in the step (2), 300g of nano calcium carbonate, 150g of PVC powder, 20g of fumed silica and 20g of carbon black into a planetary stirring kettle, uniformly stirring under the vacuum state of-0.098 Mpa, keeping the stirring and mixing temperature at less than 50 ℃, then removing the vacuum by using dry nitrogen, sequentially adding 1g of curing accelerator, 4g of bonding accelerator and 5g of dewatering stabilizer, decompressing and evacuating, removing bubbles under the vacuum state of-0.098 Mpa, then removing the vacuum by using dry nitrogen, pouring, preparing solvent-resistant epoxy modified polyurethane bonding sealant, and loading into a closed container.
In the step (1), the preparation method of the epoxy modified polyether triol comprises the following steps: 150g of polyethylene glycol (with a relative molecular weight of 500) and 29.7g of glycidyl ether epoxy resin are added into a dry 1L four-mouth bottle, the temperature is raised to 80 ℃, 0.9g of catalyst boron trifluoride is added, the reaction is carried out for 4 hours at a constant temperature, after infrared detection, the reaction is terminated after the epoxy group peak completely disappears, the temperature is reduced, and the epoxy modified polyether triol is prepared.
Wherein the glycidyl ether epoxy resin is triglycidyl isocyanurate.
In the step (1), the polyether triol is a polyoxypropylene triol.
In the step (2), the polyether glycol is polyoxypropylene glycol having an average molecular weight of 1500.
In the step (3), the nano calcium carbonate, the PVC powder, the fumed silica and the carbon black are all dried in advance until the moisture content is less than 500 ppm.
In the step (3), the curing accelerator is dibutyltin dilaurate; the adhesion promoter is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane; the water removal stabilizer is p-toluenesulfonyl isocyanate.
Example 6
A preparation method of solvent-resistant epoxy modified polyurethane sealant comprises the following steps:
step (1), preparing an epoxy modified polyurethane prepolymer A: adding 360g of epoxy modified polyether triol and 480g of polyether triol (relative molecular weight is 5000) into a dry 2L four-mouth bottle in sequence, heating to 100 ℃, carrying out vacuum dehydration for 2h, cooling to 80 ℃ after detecting that the moisture content of the liquid material is less than or equal to 100ppm, adding 280g of benzhydryl diisocyanate, carrying out heat preservation reaction for 5h under the protection of nitrogen, cooling to room temperature when the NCO value is unchanged, discharging to obtain an epoxy modified polyurethane prepolymer A, and placing the epoxy modified polyurethane prepolymer A in a dry nitrogen sealed container for later use.
Step (2), preparing a low-viscosity polyurethane prepolymer B: placing 800g of polyether glycol in a single-mouth bottle, heating to 100 ℃, vacuumizing for dehydration, cooling to room temperature after the water content is less than 100ppm, transferring to a separating funnel, and dropwise adding 240g of isophorone diisocyanate and 2 at a constant speedgThe catalyst stannous octoate mixture is added into a four-neck flask, the dropping speed is controlled to be 1h, the constant temperature reaction is carried out for 6h under the protection of nitrogen at the temperature of 80 ℃, when the NCO value is unchanged, the temperature is reduced to room temperature, the material is discharged, the low-viscosity polyurethane prepolymer B is prepared, and the low-viscosity polyurethane prepolymer B is placed in a dry nitrogen closed container for standby.
Step (3), preparing the epoxy modified polyurethane sealant: adding 280 parts into a planetary stirring kettlegEpoxy modified polyurethane prepolymer A, 220 prepared in step (1)gThe low-viscosity polyurethane prepolymer B, 300 prepared in the step (2)gStirring nano calcium carbonate, 150g of PVC powder, 20g of fumed silica and 20g of carbon black uniformly under the vacuum state of-0.098 Mpa, stirring and mixing the components, keeping the temperature to be less than 50 ℃, then removing the vacuum by using dry nitrogen, sequentially adding 1g of curing accelerator, 4g of adhesion accelerator and 5g of dewatering stabilizer, vacuumizing under reduced pressure, removing bubbles under the vacuum state of-0.098 Mpa, removing the vacuum by using dry nitrogen, pouring out, and obtaining the solvent-resistant epoxy modified polyurethane adhesive sealant, and loading the solvent-resistant epoxy modified polyurethane adhesive sealant into a closed container.
In the step (1), the preparation method of the epoxy modified polyether triol comprises the following steps: adding 600g of polyethylene glycol (with a relative molecular weight of 2000) and 29.7g of glycidyl ether epoxy resin into a dry 1L four-mouth bottle, heating to 80 ℃, adding 0.9g of catalyst boron trifluoride, reacting for 4 hours at a constant temperature, stopping the reaction after an epoxy group peak completely disappears through infrared detection, cooling and discharging to obtain the epoxy modified polyether triol.
Wherein the glycidyl ether epoxy resin is triglycidyl isocyanurate.
In the step (1), the polyether triol is a polyoxypropylene triol.
In the step (2), the polyether glycol is a polyoxypropylene glycol having an average molecular weight of 2000.
In the step (3), the nano calcium carbonate, the PVC powder, the fumed silica and the carbon black are all dried in advance until the moisture content is less than 500 ppm.
In the step (3), the curing accelerator is dibutyltin dilaurate; the adhesion promoter is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane; the water removal stabilizer is p-toluenesulfonyl isocyanate.
Comparative example 1
A preparation method of a polyurethane sealant comprises the following steps:
step (1), preparing a polyurethane prepolymer C: adding 840g of polyether triol (relative molecular weight 5000) into a dry 2L four-mouth bottle, heating to 100 ℃, vacuum dehydrating for 2h, detecting that the water content of the liquid material is less than or equal to 100ppm, cooling to 80 ℃, adding 160g of benzhydryl diisocyanate, carrying out heat preservation reaction for 5h under the protection of nitrogen, cooling to room temperature when the NCO value is unchanged, discharging to obtain an epoxy modified polyurethane prepolymer A, and placing the epoxy modified polyurethane prepolymer A in a dry nitrogen sealed container for later use.
Step (2), preparing a low-viscosity polyurethane prepolymer B: placing 800g of polyether glycol in a single-neck bottle, heating to 100 ℃, vacuumizing for dehydration, cooling to room temperature after the moisture content is less than 100ppm, transferring to a separating funnel, dropwise adding into a four-neck flask containing a mixture of 240g of isophorone diisocyanate and 2g of catalyst stannous octoate at a constant speed, controlling the dropwise adding speed at 1h, reacting at a constant temperature of 80 ℃ for 6h under the protection of nitrogen, cooling to room temperature when the NCO value is unchanged, discharging to obtain a low-viscosity polyurethane prepolymer B, and placing in a dry nitrogen sealed container for later use.
Step (3), preparing the polyurethane sealant: adding 280g of the polyurethane prepolymer C prepared in the step (1), 220g of the low-viscosity polyurethane prepolymer B prepared in the step (2), 300g of nano calcium carbonate, 150g of PVC powder, 20g of fumed silica and 20g of carbon black into a planetary stirring kettle, uniformly stirring under the vacuum state of-0.098 Mpa, keeping the stirring and mixing temperature at less than 50 ℃, then removing the vacuum by using dry nitrogen, sequentially adding 1g of curing accelerator, 4g of bonding accelerator and 5g of water removal stabilizer, decompressing, evacuating, removing bubbles under the vacuum state of-0.098 Mpa, then removing the vacuum by using dry nitrogen, discharging, pouring, and preparing the polyurethane bonding sealant, and loading into a closed container.
In the step (2), the polyether glycol is polyoxypropylene glycol having an average molecular weight of 500.
In the step (3), the nano calcium carbonate, the PVC powder, the fumed silica and the carbon black are all dried in advance until the moisture content is less than 500 ppm.
In the step (3), the curing accelerator is dibutyltin dilaurate; the adhesion promoter is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane; the water removal stabilizer is p-toluenesulfonyl isocyanate.
Comparative example 2
A preparation method of solvent-resistant epoxy modified polyurethane sealant comprises the following steps:
step (1), preparing an epoxy modified polyurethane prepolymer A: adding 360g of epoxy modified polyether triol and 480g of polyether triol (relative molecular weight is 5000) into a dry 2L four-mouth bottle in sequence, heating to 100 ℃, carrying out vacuum dehydration for 2h, cooling to 80 ℃ after detecting that the moisture content of the liquid material is less than or equal to 100ppm, adding 280g of benzhydryl diisocyanate, carrying out heat preservation reaction for 5h under the protection of nitrogen, cooling to room temperature when the NCO value is unchanged, discharging to obtain an epoxy modified polyurethane prepolymer A, and placing the epoxy modified polyurethane prepolymer A in a dry nitrogen sealed container for later use.
Step (2), preparing the epoxy modified polyurethane sealant: adding 280g of the epoxy modified polyurethane prepolymer A prepared in the step (1), 220g of dioctyl phthalate, 300g of nano calcium carbonate, 150g of PVC powder, 20g of fumed silica and 20g of carbon black into a planetary stirring kettle, uniformly stirring under the vacuum state of-0.098 Mpa, keeping the stirring and mixing temperature to be less than 50 ℃, then relieving the vacuum by using dry nitrogen, sequentially adding 1g of curing accelerator, 4g of bonding accelerator and 5g of dewatering stabilizer, vacuumizing under reduced pressure, removing bubbles under the vacuum state of-0.098 Mpa, then relieving the vacuum by using dry nitrogen, pouring to prepare the epoxy modified polyurethane sealant, and loading the epoxy modified polyurethane sealant into a closed container.
In the step (1), the preparation method of the epoxy modified polyether triol comprises the following steps: 150g of polyethylene glycol (with a relative molecular weight of 500) and 29.7g of glycidyl ether epoxy resin are added into a dry 1L four-mouth bottle, the temperature is raised to 80 ℃, 0.9g of catalyst boron trifluoride is added, the reaction is carried out for 4 hours at a constant temperature, after infrared detection, the reaction is terminated after the epoxy group peak completely disappears, the temperature is reduced, and the epoxy modified polyether triol is prepared.
Wherein the glycidyl ether epoxy resin is triglycidyl isocyanurate.
In the step (1), the polyether triol is a polyoxypropylene triol.
In the step (2), the nano calcium carbonate, the PVC powder, the fumed silica and the carbon black are all dried in advance until the moisture content is less than 500 ppm.
In the step (2), the curing accelerator is dibutyltin dilaurate; the adhesion promoter is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane; the water removal stabilizer is p-toluenesulfonyl isocyanate.
Comparative example 3
A preparation method of epoxy modified polyurethane sealant comprises the following steps:
step (1), preparing an epoxy modified polyurethane prepolymer A: sequentially adding 200g of epoxy modified polyether triol and 640g of polyether triol (relative molecular weight of 5000) into a dry 2L four-mouth bottle, heating to 100 ℃, carrying out vacuum dehydration for 2h, cooling to 80 ℃ after detecting that the moisture content of the liquid material is less than or equal to 100ppm, adding 225g of benzhydryl diisocyanate, carrying out heat preservation reaction for 5h under the protection of nitrogen, cooling to room temperature when the NCO value is unchanged, discharging to obtain an epoxy modified polyurethane prepolymer A, and placing the epoxy modified polyurethane prepolymer A in a dry nitrogen sealed container for later use.
Step (2), preparing a low-viscosity polyurethane prepolymer B: placing 800g of polyether glycol in a single-neck bottle, heating to 100 ℃, vacuumizing for dehydration, cooling to room temperature after the moisture content is less than 100ppm, transferring to a separating funnel, dropwise adding into a four-neck flask containing a mixture of 240g of isophorone diisocyanate and 2g of catalyst stannous octoate at a constant speed, controlling the dropwise adding speed at 1h, reacting at a constant temperature of 80 ℃ for 6h under the protection of nitrogen, cooling to room temperature when the NCO value is unchanged, discharging to obtain a low-viscosity polyurethane prepolymer B, and placing in a dry nitrogen sealed container for later use.
Step (3), preparing the epoxy modified polyurethane sealant: adding 280g of the epoxy modified polyurethane prepolymer A prepared in the step (1), 220g of the low-viscosity polyurethane prepolymer B prepared in the step (2), 300g of nano calcium carbonate, 150g of PVC powder, 20g of fumed silica and 20g of carbon black into a planetary stirring kettle, uniformly stirring under the vacuum state of-0.098 Mpa, keeping the stirring and mixing temperature at less than 50 ℃, then removing the vacuum by using dry nitrogen, sequentially adding 1g of curing accelerator, 4g of bonding accelerator and 5g of water removal stabilizer, vacuumizing under reduced pressure, removing bubbles under the vacuum state of-0.098 Mpa, then removing the vacuum by using dry nitrogen, pouring, preparing the solvent-resistant epoxy modified polyurethane bonding sealant, and loading the solvent-resistant epoxy modified polyurethane bonding sealant into a closed container.
In the step (1), the preparation method of the epoxy modified polyether triol comprises the following steps: 150g of polyethylene glycol (with a relative molecular weight of 500) and 29.7g of glycidyl ether epoxy resin are added into a dry 1L four-mouth bottle, the temperature is raised to 80 ℃, 0.9g of catalyst boron trifluoride is added, the reaction is carried out for 4 hours at a constant temperature, after infrared detection, the reaction is terminated after the epoxy group peak completely disappears, the temperature is reduced, and the epoxy modified polyether triol is prepared.
Wherein the glycidyl ether epoxy resin is triglycidyl isocyanurate.
In the step (1), the polyether triol is a polyoxypropylene triol.
In the step (2), the polyether glycol is polyoxypropylene glycol having an average molecular weight of 1000.
In the step (3), the nano calcium carbonate, the PVC powder, the fumed silica and the carbon black are all dried in advance until the moisture content is less than 500 ppm.
In the step (3), the curing accelerator is dibutyltin dilaurate; the adhesion promoter is gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane; the water removal stabilizer is p-toluenesulfonyl isocyanate.
The polyurethane sealants prepared in the above examples 1 to 6 and comparative examples 1 to 3 were subjected to solvent resistance tests (i) to (ninthly), and the performances of the polyurethane sealants before and after the soaking in the solvent were tested.
The test method comprises the following steps: according to the chemical corrosion resistance test of the coating in the industrial standard GB/T6968-: in 2006, reference gasoline B (equivalent to a mixture of 30% of toluene and 70% of isooctane by volume) is used as a standard solvent, the sealant (i-nini) and a special polyurethane instrument glue of a certain commercial brand are respectively tested, the change trends of mechanical property, hardness, mass change and volume swelling are observed, the test period is 7d, the temperature is 23 ℃ and the humidity is RH 50% (reference to method A8.3 in ISO 2812-1: 2017).
The test results are shown below:
Figure BDA0002052982270000231
the comparison of the data shows that the epoxy modified polyurethane adhesive sealant prepared by the invention has better chemical corrosion resistance and mechanical property, the mass change rate and the volume change rate can keep smaller change rate after being soaked in the solvent, the adhesive sealing effect is good, and the epoxy modified polyurethane adhesive sealant can also keep good adhesive sealing effect in the long-term use process when being used for a gas meter.
In addition, (1) compared with the sealant (I) in the embodiment 1, the sealant (IV) prepared in the embodiment 4 has the advantages that the proportion of the epoxy modified polyurethane prepolymer A in the sealant is increased, and the mechanical property, the mass change rate and the volume change rate of the prepared sealant after being soaked in a solvent are relatively reduced; (2) compared with the sealant I in the embodiment 1, the epoxy modified polyurethane prepolymer A in the sealant has a smaller proportion, and the mechanical property, the mass change rate and the volume change rate of the prepared sealant soaked by the solvent are relatively increased; (3) compared with the sealant I in the embodiment 1, the sealant prepared in the embodiment 6 has a large molecular weight of polyethylene glycol in epoxy modified polyether triol, and the mechanical property, the mass change rate and the volume change rate of the prepared sealant soaked in the solvent are relatively increased.
From the above examples 4-6, it can be seen that, on the premise of not significantly changing the basic performance of the sealant, the formula is adjusted within a reasonable range, and the ratio of the epoxy modified polyurethane prepolymer a in the sealant is increased, the ratio of the epoxy modified polyether triol in the epoxy modified polyurethane prepolymer a is increased, and the molecular weight of the polyethylene glycol is reduced, which all have a gain effect on the solvent resistance of the sealant.
Compared with the embodiment 1, the polyether triol is not subjected to epoxy modification, the epoxy modified polyether triol is not adopted in the polyurethane prepolymer, and the prepared sealant is remarkably improved in mechanical property, mass change rate and volume change rate after being soaked in the solvent; the introduction of the epoxy modified polyurethane prepolymer A into the polyurethane sealant of the invention results in a more obvious solvent resistance increasing effect of the sealant, and the solvent resistance of the sealant can be greatly improved.
Compared with the example 1, the comparative example 2 does not adopt the low-viscosity polyurethane prepolymer B, but adopts the traditional dioctyl phthalate, and the prepared sealant (after being soaked by the solvent) has the advantages of obviously increased mechanical property, mass change rate and volume change rate, even larger change rate compared with the change rate of the comparative example 1 and weaker solvent resistance; the polyurethane sealant of the invention has the advantages that the polyurethane prepolymer B is used for replacing the traditional dioctyl phthalate, the solvent resistance increasing effect of the sealant is obvious, and the solvent resistance of the sealant can be greatly improved.
Compared with the embodiment 1, the epoxy modified polyether triol in the epoxy modified polyurethane prepolymer A is less than 20%, the mechanical property, the mass change rate and the volume change rate of the prepared sealant after being soaked in the solvent are obviously increased, and the solvent resistance of the sealant is poorer; the polyurethane sealant of the invention can ensure that the prepared epoxy modified polyurethane prepolymer A has excellent cohesive energy strength and mechanical property and can obviously improve the solvent resistance of the sealant by strictly controlling the weight percentage of the epoxy modified polyether triol to be 20-45%.
The index changes of the polyurethane sealant sold in the market are the largest, which shows that the epoxy modified polyurethane adhesive sealant prepared by the invention has better chemical corrosion resistance and mechanical property, the mass change rate and the volume change rate can keep smaller change rates after being soaked in a solvent, the adhesive sealing effect is good, and the adhesive sealing effect can be kept very good even in the long-term use process when the adhesive sealant is used for a gas meter.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.

Claims (6)

1. A solvent-resistant epoxy modified polyurethane sealant is characterized in that: the sealant comprises the following raw materials in percentage by weight:
Figure FDA0003052439210000011
the epoxy modified polyurethane prepolymer A is an NCO-terminated polymer prepared by reacting the following raw materials in percentage by weight: 15-40% of polyether triol, 20-45% of epoxy modified polyether triol and 20-40% of diisocyanate; wherein the molar ratio of isocyanate group to hydroxyl group of the epoxy modified polyurethane prepolymer A is 2.0-3.0: 1;
the low-viscosity polyurethane prepolymer B is an NCO-terminated polymer prepared by reacting the following raw materials in percentage by weight: 40-80% of polyether glycol and 20-60% of diisocyanate; wherein the molar ratio of isocyanate group to hydroxyl group of the low-viscosity polyurethane prepolymer B is 2.5-3.0: 1; the viscosity of the low-viscosity polyurethane prepolymer B is 1000-3000mPa & s;
the inorganic filler is at least one of nano calcium carbonate, kaolin, silica micropowder and carbon black, and is dried in advance until the moisture content is less than 500 ppm; the thixotropic agent is at least one of fumed silica, polyurea, bentonite and PVC powder, and is dried in advance until the moisture content is less than 500 ppm; the water removal stabilizer is at least one of oxazolidine water removal agent, p-methyl benzenesulfonyl isocyanate and triethyl orthoformate;
the curing accelerator is at least one of an organic tin catalyst, a tertiary amine catalyst, an organic zinc catalyst and an organic bismuth catalyst; the adhesion promoter is at least one of epoxy silane coupling agent, amino silane coupling agent and mercapto silane coupling agent.
2. The solvent-resistant epoxy modified polyurethane sealant as claimed in claim 1, wherein: the polyether triol is polyoxypropylene triol with the average molecular weight of 2000-6000; the diisocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate and p-phenylene diisocyanate.
3. The solvent-resistant epoxy modified polyurethane sealant as claimed in claim 1, wherein: the epoxy modified polyether triol is an OH-terminated compound prepared by the reaction of trifunctional glycidyl epoxy resin and polyethylene glycol, wherein the molar ratio of epoxy groups to hydroxyl groups is 1: 1.5-2.5; the trifunctional glycidyl epoxy resin is glycidyl ether epoxy resin or glycidyl amine epoxy resin; the molecular weight of the polyethylene glycol is 500-3000.
4. The solvent-resistant epoxy modified polyurethane sealant as claimed in claim 1, wherein: the polyether diol is polyoxypropylene diol with the average molecular weight of 500-2000; the diisocyanate is at least one of toluene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.
5. The solvent-resistant epoxy modified polyurethane sealant as claimed in claim 1, wherein: the organic tin catalyst is at least one of dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, alkyl tin dithiolate, dioctyltin mercaptide and dialkyl tin dimaleate; the tertiary amine catalyst is at least one of N, N-dimethylcyclohexylamine, triethanolamine, dimethylethanolamine, triethylamine and triethylenediamine; the organic zinc catalyst is at least one of zinc isooctanoate, zinc neodecanoate and zinc naphthenate; the organic bismuth catalyst is at least one of bismuth isooctanoate, bismuth laurate, bismuth neodecanoate and bismuth naphthenate; the epoxy silane coupling agent is at least one of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, 3- (2, 3-epoxypropoxy) propyl methyl diethoxy silane, 2- (3, 4-epoxycyclohexyl) ethyl triethoxy silane and 2- (3, 4-epoxycyclohexyl) ethyl trimethoxy silane; the amino silane coupling agent is at least one of gamma-aminopropyl triethoxysilane, N-beta (aminoethyl) -gamma-aminopropyl trimethoxysilane, anilinomethyl triethoxysilane and N-beta (aminoethyl) -gamma-aminopropyl methyl diethoxy silane; the mercaptosilane coupling agent is gamma-mercaptopropyltrimethoxysilane.
6. A process for preparing the solvent resistant epoxy modified polyurethane sealant according to any one of claims 1 to 5, which comprises: the method comprises the following steps:
step (1), preparing an epoxy modified polyurethane prepolymer A: according to the weight percentage, mixing polyether triol and epoxy modified polyether triol, heating to 110 ℃ with temperature, vacuumizing to remove water, cooling to 80-90 ℃, adding diisocyanate, reacting under the protection of nitrogen, and cooling to room temperature until the NCO value is unchanged to obtain epoxy modified polyurethane prepolymer A;
step (2), preparing a low-viscosity polyurethane prepolymer B: heating polyether glycol to 110 ℃ according to the weight percentage, vacuumizing to remove water, cooling to room temperature, slowly and uniformly dripping the polyether glycol into diisocyanate, controlling the dripping time to be 0.8-1.2h, reacting for 4-6h under the protection of nitrogen at the temperature of 80-90 ℃, and cooling to room temperature when the NCO value is unchanged to prepare a low-viscosity polyurethane prepolymer B;
step (3), preparing the epoxy modified polyurethane sealant: according to the weight percentage, uniformly stirring the epoxy modified polyurethane prepolymer A prepared in the step (1), the low-viscosity polyurethane prepolymer B prepared in the step (2), the inorganic filler and the thixotropic agent under the vacuum state of-0.098 to-0.1 Mpa, keeping the mixing temperature at 10-50 ℃, then sequentially adding the curing accelerator, the adhesion accelerator and the dewatering stabilizer, removing bubbles under the vacuum state of-0.098 to-0.1 Mpa after uniformly stirring, and removing the vacuum by using dry nitrogen gas to prepare the solvent-resistant epoxy modified polyurethane adhesive sealant.
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